KR100551600B1 - Production process of copper phthalocyanine in the beta modification - Google Patents

Abstract

The present invention provides a process for the production of pigmentary copper phthalocyanine in the beta crystalline phase comprising:a) dry or aqueous milling of crude copper phthalocyanine in combination with a natural or chemically modified resin and, optionally, a grinding auxiliary followed by;b) isolation of the milled mass followed by;c) conditioning treatment of the milled mass.

Description

Production process of copper phthalocyanine in the beta modification             

The present invention relates to a process for the preparation of copper phthalocyanine pigment compositions useful for the coloring of surface coatings, in particular oil ink formulations used in printing.

The crude copper phthalocyanine is ground in the presence of a grinding aid such as an organic / inorganic salt, followed by separate solvent treatment with a partially water miscible solvent as described in British Patent 1140836, or as described in US Pat. No. 5449774. Likewise, methods are known for producing copper phthalocyanine pigments by separately aqueous emulsion treatment of the ground material with a liquid amine in the presence of a surfactant such as an alkali metal salt of wood rosin. If the solvent treatment step involves the use of polar aliphatic solvents, as described in British Patent No. 1140836, the initial dry (almost free of liquid) grinding step may be a high proportion of grinding aids (eg organic / inorganic). Salt), usually 2 parts of grinding aid per 1 part of crude copper phthalocyanine.

Surprisingly, according to the present invention, the crude copper phthalocyanine is pulverized with a natural resin or chemically modified resin and then subjected to separate solvent conditioning or aqueous latex conditioning to the process of British Patent 1140836 or US Pat. No. 5449774. It has thus been found that a copper phthalocyanine composition is obtained which exhibits excellent pigment properties compared to the resulting pigment composition. In particular, the copper phthalocyanine composition of the present invention improves color intensity, gloss and dispersibility, especially when formulated in oil ink formulations. In addition, the process according to the invention significantly reduces the amount of conventional grinding aids, such as organic / inorganic salts, compared to the process of British patent 1140836 when the subsequent conditioning step involves a solvent. When using the method of the present invention, the pigment material is treated more efficiently and effectively than the method described in British Patent 1140836.

Summary of the Invention

Accordingly, the present invention provides a process for dry or wet milling crude copper phthalocyanine with a natural or chemically modified resin and optionally a grinding aid (a), separating the ground material (b) and conditioning the ground material. It provides a method for producing a pigment copper phthalocyanine on the beta crystals, comprising the step (c).

Explanation

As an essential step in the process according to the invention, the crude copper phthalocyanine is co-milled with a natural resin or chemically modified resin and optionally with a grinding aid. For copper phthalocyanine as defined herein, "crude" means that the nonpigment size is typically at least about 10 μm.

Crude copper phthalocyanine is reacted at elevated temperatures of phthalic anhydride with urea and copper salts in the presence of a catalytic amount of a transition metal compound such as ammonium molybdate (the reaction is carried out in a high boiling aromatic solvent such as nitrobenzene or without solvent Under the "dry-baking" method). Standard methods for the preparation of crude copper phthalocyanine are detailed in "Phthalocyanine Compounds" by Moser and Thomas, Reinhold Publishing Corporation 1963, which is incorporated herein by reference.

Resins suitable for use in the process of the invention include rosin, the main component of which is abiotic acid; Chemically modified rosin such as hydrogenated rosin, dehydrogenated rosin unbalanced rosin; Dimerized or polymerized rosin; Partially esterified rosin; Rosin or rosin derivatives and mixtures thereof polymerized with materials such as maleic or phenolic modified rosin and formaldehyde which are not esterified or partially esterified. Preferred resins for use in the present invention are Stabelite ^R resins (hydrogenated rosin) sold by Hercules (USA) and Recoldis A resins sold by Langley Smith in the UK. (Recoldis A resin ^R ) (unbalanced rosin) and Dymerex ^R resin (dimerized rosin) commercially available from Hercules. In the grinding step, the natural resin or chemically modified resin is generally from about 1 to about 15% by weight, preferably from about 2 to about 5% by weight, based on the weight of the crude copper phthalocyanine charged to the grinding device. Present in quantities. Preferred resins in the present invention are hydrogenated rosin and unbalanced rosin.

Grinding aid as defined herein means all materials used to aid in the size reduction of copper phthalocyanine from crude copper phthalocyanine to pigment copper phthalocyanine using abrasion / grinding techniques. Grinding aids suitable for use in the process of the invention include calcium chloride, sodium chloride, sodium sulfate, sodium formate, sodium acetate or other organic or inorganic salts, phthalimide or phthalic anhydride and mixtures thereof. Preferred grinding aids in the present invention are sodium formate, sodium chloride and sodium acetate. When the grinding is carried out in a dry grinding technique, the grinding aid is in an amount of about 2 to about 15% by weight, preferably about 6 to about 8% by weight, based on the weight of the crude copper phthalocyanine charged to the grinding device. exist.

Grinding as defined herein means a method in which solids are applied to abrasion, grinding, etc. to reduce particle size. Dry grinding as defined herein means a method of applying a solid to abrasion, grinding or the like to reduce particle size with little liquid. However, as detailed later in this specification, a small amount of solvent (or amine) may be added during the milling step. The grinding of the crude copper phthalocyanine and resin mixtures of the present invention can be carried out by dry or wet techniques. If the grinding is carried out by a dry technique, a suitable device may be a ball mill or a vibration mill. If the grinding is carried out in an aqueous medium, the apparatus used is conveniently a bead mill. If the grinding is carried out in an aqueous medium, no grinding aid is required.

As another essential step in the process according to the invention, the ground mixture (a mixture of crude copper phthalocyanine, a resin and optionally a grinding aid) is separated. If the milling step is essentially a dry process, the milled material can be separated by direct release from the milling apparatus. If the grinding is carried out by wet grinding technique, the ground material is separated into powder form. However, in the case where the conditioning of the ground material is carried out in an emulsion process, the ground material produced by the wet grinding technique can optionally be separated in the form of a "filter cake" and used in subsequent emulsion conditioning steps.

As another essential step in the process of the invention, a separate grinding mixture of crude copper phthalocyanine, a resin and optionally a grinding aid is conditioned by treatment with a solvent, emulsion or carboxylic acid.

If conditioning is carried out by treatment with a solvent, the milled material is added dropwise or added all at once and dispersed in the solvent by stirring until it is completely “wet” to bring all dry material into contact with the solvent. The aqueous resin solution can be added in this step in an amount of 0 to about 10% by weight, preferably about 1 to about 5% by weight of crude copper phthalocyanine. The resulting slurry is then heated to a temperature in the range of about 50 ° C. to the boiling point of the solvent. Solvent treatment is carried out for a time sufficient to convert the pigment copper phthalocyanine to nearly β crystal modification. These phase changes can be routinely monitored using standard analytical techniques such as infrared absorption spectroscopy. Determination of the settings needed to determine characteristic peaks for the α and β forms are common experimental content. The temperature and time required to effect this change from α to β depends on the crystallization action of the solvent which can cause a phase change in a short time at room temperature, for example chloroform. After such solvent conditioning, typically beta copper in pigment form by first contacting with a dilute inorganic acid such as hydrochloric acid or a dilute base such as potassium hydroxide to assist in solvent removal, followed by filtration or centrifugation to remove the solvent. Phthalocyanine is separated from the material. If the solvent is water miscible, water may be added at the end of the solvent conditioning step and the solvent removed by azeotropic distillation. The product can then be separated by conventional filtration and drying techniques.

Preferred solvents for use in the present invention are polar aliphatic solvents. Suitable solvents for use in the process of the invention can be selected from a wide variety of chemical types, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, pentanol or other lower alcohols. ; Ethyl acetate or other lower alkyl monocarboxylates; Acetone, methyl ethyl ketone, methyl isobutyl ketone or other dialkyl ketones; 2-methoxy ethanol, 2-ethoxy ethanol or other lower alkoxy alkanols; Ethylene glycol, diethylene glycol or other alkylene glycols and mixtures thereof.

Preference is also given to mixtures of lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, pentanol or other lower alcohols with water. Preferred lower alcohols for such mixtures are n-propanol, isopropanol, n-butanol or isobutanol, in particular n-butanol or iso-butanol. n-butanol is very preferred as lower alcohol. These mixtures preferably contain at least 50% by weight, in particular at least 75% by weight of water. An important mixture is a mixture containing 80 to 98% by weight of water and 2 to 20% by weight of lower alcohol, in particular a mixture containing 90 to 95% by weight of water and 5 to 10% by weight of lower alcohol.

More preferred solvents in the present invention are solvents that are at least partially water miscible and capable of forming an azeotropic mixture with water. In such a case, the polar aliphatic solvent may contain dissolved water in a proportion insufficient to separate into two phases. The solvent may generally be used in an amount of 200 to 1000%, preferably 400 to 800%, based on the weight of the starting material to be ground (crude copper phthalocyanine, resin and any grinding aid). In addition, the proportion of solvent (typically 1 to 5%) used for the solvent treatment can optionally be incorporated in the grinding step described above.

Preferred carboxylic acids for use in the present invention are 2-ethyl hexanoic acid, oleic acid, caproic acid, valeric acid or other C ₄ -C ₂₀ straight or branched chain aliphatic carboxylic acids and mixtures thereof. Carboxylic acids can generally be used in amounts of 200 to 1000%, preferably 400 to 800%, based on the weight of the starting material to be ground (crude copper phthalocyanine, resins and optional grinding aids). In addition, the proportion of carboxylic acid (typically 1 to 5%) used for the conditioning treatment can optionally be incorporated in the grinding step described above.

The emulsion conditioning treatment of the milled material (dry powder or wet milled dispersion or "filter-cake") is carried out by mixing an emulsion containing liquid C ₆ -C ₂₀ amine in water with an additional amount of resin salt. Typically, the resin salt is present in an amount of 0 to 10% by weight, preferably about 1 to about 5% by weight of crude copper phthalocyanine. The liquid amines can be mono-, di- or tri-amines and can be aliphatic or aromatic in nature. Examples of suitable amines are C ₇ -C ₁₆ alkyl mono amines and aliphatic diamines of the formula RNH.CHCH ₂ CH ₂ CH ₂ NH ₂ , wherein R is a C ₁₂ -C ₁₆ aliphatic radical such as a Uji or coco (lauryl) radical Is). Aryl amines include aniline and C ₁ -C ₄ alkyl substituted anilines, such as o-toluidine, N, N-diethylaniline and N, N-dimethylaniline. The amount of amine used may generally be about 2 to about 50 weight percent, preferably about 5 to about 30 weight percent, based on the weight of copper phthalocyanine contained in the milled material. In addition, the proportion of amine (typically from about 1 to about 20%) used in the latex treatment step may optionally be incorporated into the grinding step described above. The emulsification step is assisted by adding alkali or potassium hydroxide to produce alkali metal salts of natural resins or chemically modified resins. The mixing of the ground material in the emulsion treatment is generally carried out at elevated temperatures, for example at a temperature in the range from 20 to 100 ° C., preferably from 40 to 70 ° C., and for a time sufficient to cause the pigment copper phthalocyanine to be almost β crystal modified. do.

After the emulsion treatment is completed, as assessed by the conversion of the α crystalline form of copper phthalocyanine from the α crystal form to the β crystal form, the mixture is preferably made acidic by adding an inorganic acid to lower the pH of the mixture to less than 1.5. Acidifying the mixture has a dual effect. First, the amine used in the emulsion treatment can be removed from the final pigment by filtration / washing by modifying it with an amine salt that is soluble in the aqueous phase. Second, the natural or chemically modified resins are regenerated in the free acid form. Additional standard analytical techniques, such as electron microscopy, can be used to measure particle size and evaluate the crystalline form at this stage. After acidification, the pigment slurry can be filtered, washed with water and then dried. The copper phthalocyanine pigments obtained with the β crystal modified bodies according to the present invention exhibit excellent color strength, gloss and dispersibility compared to similar products in which the incorporation of natural resins or chemically modified resins is made after the grinding step. In addition, the copper phthalocyanine pigments obtained by "dry grinding / solventing" the components of the present invention exhibit significantly improved process throughput by significantly reducing the amount of grinding aid required for the dry grinding step.

The copper phthalocyanine pigments produced by the present invention are particularly suitable for oil ink articles. Pigment products are also useful as colorants in published gravure inks, paints and plastics. In order to improve performance in gravure ink, paint or plastic systems, up to about 20% by weight, preferably up to about 10% by weight, more preferably about 1 to about 5% by weight additives which may be derivatives of copper phthalocyanine % Can be added to the pigment product obtained according to the invention in any step. Examples of such additives include dimethylaminomethyl copper phthalocyanine or phthalimidomethyl copper phthalocyanine, in which the number of substituent groups on the copper phthalocyanine molecule is in the range of 1 to 4, preferably 2 to 3; Sulfonated copper phthalocyanine; Or amine salts of sulfonated copper phthalocyanine and mixtures thereof.

The following non-limiting examples further illustrate the invention.

Example 1

Preparation of heatset oil ink from copper phthalocyanine comprising hydrogenated rosin added to the conditioning step

A mixture of 93.2 g of crude copper phthalocyanine and 6.8 g of sodium formate is ground in a 0.6 L vibrating ball mill until the phase change indicates a content of 50 to about 75%. α content is monitored by infrared absorption spectroscopy detailed above. 250 g of water, 15.3 g of 50% potassium hydroxide solution and 40 g of hydrogenated wood rosin are stirred until a solution is formed. Then water is added until the volume of the solution reaches 267 ml. The pulverized copper phthalocyanine mixture is added to 200 ml of IPS2 (83% isopropyl alcohol and 17% water) supplied by Charles Tennant, UK, and 10.5 g of the hydrogenated wood rosin solution mentioned above. The colored slurry is then stirred at the reflux temperature of the solvent for about 4 hours and then 200 ml of water is added. The solvent fraction of the slurry is distilled off. After distillation, 30 ml of 36% hydrochloric acid is added to the slurry. The acidified slurry was filtered using a Buchner apparatus, washed with water until the pigment contained little acid and formate ions (less than about 1000 micro Siemens), and the resulting β-form pigment was washed with moisture. It is dried at about 75 ° C. until it is almost free (less than about 1% moisture).

20 g of the pigment in β form thus obtained are premixed with 80 g of a conventional heatset oil ink varnish. 100 g of the premix are crushed three rolls with a Buhler SDY-200 three roll mill at 23 ° C. for about 5 minutes.

First dispersion pass at 10 bar (1000 KPa)

2nd dispersion pass at 25 bar (2500 KPa)

Third dispersion pass at 25 bar (2500 KPa)

Of the heatset oil ink obtained by reducing the third pass ink (20% coloration) to 14% pigment using the varnish above and printing using a Prufbau ^R printer to provide a print with different film weights. Evaluate the characteristics. Conventional heatset oil inks as defined herein contain a mixture of modified phenolic resins, alkyd resins, petroleum distillates and 0-5% preparations. The print density for each print (different film weight) is measured using a densitometer (eg Gretag D19C). Gloss is measured at 60 ° using Erichsen Mini glossmaster ^R at the same film weight.

Example 2

Preparation of heatset oil ink from copper phthalocyanine comprising hydrogenated rosin added to the conditioning step

The method of Example 1 is repeated but 21.0 g of hydrogenated wood rosin solution is added instead of 10.5 g.

The heatset oil ink of Example 2 was evaluated as described above in Example 1.

Example 3

Preparation of heatset oil ink from copper phthalocyanine comprising hydrogenated rosin added to the grinding step

A mixture of 91.0 g of crude copper phthalocyanine, 2.3 g of hydrogenated wood rosin and 6.7 g of sodium formate is ground in a ball mill until the phase change indicates an α content of about 50 to about 75%. 70 g of the pulverized copper phthalocyanine mixture is added to 200 ml of IPS2 (83% isopropyl alcohol and 17% water) together with 10 ml of 50% potassium hydroxide solution. The colored slurry is then stirred for about 4 hours with reflux and then 200 ml of water is added. The IPS2 fraction of the slurry is distilled off. Finally, 25 ml of 36% hydrochloric acid is added. The acidified slurry is filtered and washed with water until the pigment contains no acid and formate ions, and then the β pigment is dried at 75 ° C.

The heatset oil ink of Example 3 was evaluated as detailed above.

Example 3 is repeated, but 200 ml of a mixture of 93 wt% water and 7 wt% n-butanol is used in place of 200 ml IPS2 (83% isopropyl alcohol and 17% water).

Example 3 is repeated, but 200 ml of a mixture of 93 wt% water and 7 wt% iso-butanol is used instead of 200 ml IPS2 (83% isopropyl alcohol and 17% water).

Example 4

Preparation of heatset oil ink from copper phthalocyanine comprising hydrogenated rosin added to the conditioning step

A mixture of 93.2 g of crude copper phthalocyanine and 6.8 g of sodium formate is ground in a ball mill until the phase change indicates α content of 50 to 75%. 111 g 55 ° C. water, 11.1 g 50% potassium hydroxide solution, 2.5 g hydrogenated wood rosin and 6.1 g N, N-diethylaniline are stirred in a high speed mixer until an emulsion is obtained. The presence of latex is measured by visual analysis. 55 g of the pulverized copper phthalocyanine mixture and 150 g of 55 ° C. water are added to the emulsion. The colored emulsion is stirred at about 55 ° C. for about 4 hours. A solution of 3.6 g of calcium chloride in 42 ml of water is added and the slurry is stirred for a further about 30 minutes. Finally, 30 ml of 36% hydrochloric acid is added. The acidified slurry is filtered and washed with water until the pigment contains no acid and formate ions, and then the β pigment is dried at about 75 ° C.

The heatset oil ink of Example 4 is evaluated as described above.

Example 5

Preparation of heatset oil ink from copper phthalocyanine comprising hydrogenated rosin added to the grinding step

A mixture of 91.0 g of crude copper phthalocyanine, 2.3 g of hydrogenated wood rosin and 6.7 g of sodium formate is ground in a ball mill until the phase change indicates a content of about 50 to about 75%. 111 g 55 ° C. water, 11.1 g 50% potassium hydroxide solution, 1.3 g hydrogenated wood rosin and 6.1 g N, N-diethylaniline are stirred with a high speed mixer until an emulsion is obtained. 55 g of the pulverized copper phthalocyanine mixture and 150 g of 55 ° C. water are added to the emulsion. The colored emulsion is stirred at about 55 ° C. for about 4 hours. A solution of 3.6 g of calcium chloride in 42 ml of water is added and the slurry is stirred for a further about 30 minutes. Finally, 30 ml of 36% hydrochloric acid is added. The acidified slurry is filtered and washed with water until the pigment contains no acid and formate ions, and then the β pigment is dried at 75 ° C.

The heatset oil ink of Example 5 was evaluated as described above.

Example 6

Preparation of heatset oil ink from copper phthalocyanine comprising hydrogenated rosin added to the grinding step

A mixture of 91.0 g of crude copper phthalocyanine, 2.3 g of hydrogenated wood rosin and 6.7 g of sodium formate is ground in a ball mill until the phase change indicates a content of about 50 to about 75%. 111 g 55 ° C. water, 11.1 g 50% potassium hydroxide solution, 3.9 g hydrogenated wood rosin and 6.1 g N, N-diethylaniline are stirred with a high speed mixer until an emulsion is obtained. 55 g of the pulverized copper phthalocyanine mixture and 150 g of 55 ° C. water are added to the emulsion. The colored emulsion is stirred at about 55 ° C. for about 4 hours. A solution of 3.6 g of calcium chloride in 42 ml of water is added and the slurry is stirred for a further about 30 minutes. Finally, 30 ml of 36% hydrochloric acid is added. The acidified slurry is filtered and washed with water until the pigment contains no acid and formate ions, and then the β pigment is dried at 75 ° C.

The heatset oil ink of Example 6 was evaluated as described above.

Example 7

Preparation of Heated Oil Ink from Copper Phthalocyanine with Rubber Rosin Added to Conditioning Treatment Step

A mixture of 91.2 g of crude copper phthalocyanine and 8.8 g of calcium chloride is ground in a ball mill until the phase change indicates an α content of about 50 to about 75%. 64.3 g of the ground copper phthalocyanine mixture and 5.7 g of rubber rosin are added together with 50 ml of 50% potassium hydroxide solution to 500 ml of methyl isobutyl ketone (MIBK). The colored slurry is stirred with a high speed mixer at about 80 ° C. for about 15 minutes. The high speed mixer is then replaced with a paddle stirrer and the colored slurry is stirred at 80 ° C. for 2 hours. Finally, 30 ml of 36% hydrochloric acid is added. The acidified slurry is filtered and washed with acetone until the pigment does not contain MIBK, and then the β pigment is dried at room temperature.

The heatset oil ink of Example 7 was evaluated as described above.

Example 8

Preparation of heatset oil ink from copper phthalocyanine comprising rubber rosin added to the grinding step

A mixture of 83.8 g of crude copper phthalocyanine, 8.1 g of rubber rosin and 8.1 g of calcium chloride is ground in a ball mill until the phase change indicates an α content of about 50 to about 75%. 70 g of the ground copper phthalocyanine mixture is added to 500 ml of methyl isobutyl ketone (MIBK) together with 50 ml of 50% potassium hydroxide solution. The colored slurry is stirred with a high speed mixer at about 80 ° C. for about 15 minutes. The high speed mixer is then replaced with a paddle stirrer and the colored slurry is stirred at 80 ° C. for 2 hours. Finally, 30 ml of 36% hydrochloric acid is added. The acidified slurry is filtered and washed with acetone until the pigment does not contain MIBK, and then the β pigment is dried at room temperature.

The heatset oil ink of Example 8 was evaluated as described above.

Example 9

Preparation of Liquid Ink from Copper Phthalocyanine Including Hydrogenated Rosin Added to Conditioning Treatment Step

A pigment is prepared according to Example 1, including incorporating dimethylaminomethyl copper phthalocyanine in copper phthalocyanine at 3% by weight during the final process step.

15 g of the dried product is mixed with 80 g of phenolic varnish and 5 g of toluene for 15 minutes using a high speed mixer such as Dispermat FTS at 4000 rpm at about 60 ° C. 320 g of 2 mm glass beads are added and the mixture is dispersed at 2000 rpm for 30 minutes. Toluene is then used to reduce the millbase to 8.45% and the liquid ink of Example 9 is evaluated as described above.

Example 10

Preparation of Liquid Ink from Copper Phthalocyanine With Hydrogenated Rosin Added in the Grinding Step

A pigment is prepared according to Example 3, including incorporating dimethylaminomethyl copper phthalocyanine in copper phthalocyanine at 3% by weight during the final process step. 15 g of the dried product is mixed with 80 g of phenolic varnish and 5 g of toluene using a Dispermat FTS high speed stirrer at 4000 rpm at about 60 ° C. for about 15 minutes. 320 g of 2 mm glass beads are added and the mixture is dispersed at 2000 rpm for 30 minutes. Toluene is then used to reduce the millbase to 8.45% and the liquid ink of Example 10 is evaluated as described above.

Example 11

Preparation of heatset oil ink from copper phthalocyanine comprising an unbalanced rosin added to the conditioning treatment step

A mixture of 93.2 g of crude copper phthalocyanine and 6.8 g of sodium formate is ground in a ball mill until the phase change indicates an α content of about 50 to about 75%. 48.8 g of the pulverized copper phthalocyanine mixture is added to 1.2 g of unbalanced rosin and 300 g of 2-ethyl hexanoic acid (2-EHA). The colored slurry is then stirred with a high speed mixer at about 80 ° C. for about 1 hour. The high speed mixer is then replaced with a paddle stirrer and the colored slurry is stirred at about 80 ° C. for about 2 hours. Finally, 219 g of 33% ammonium hydroxide solution is added. The slurry is filtered and washed with acetone until the pigment does not contain 2-EHA, and then the β pigment is dried at room temperature.

The heatset oil ink of Example 11 was evaluated according to Example 1.

Example 12

Preparation of Heatset Oil Inks from Copper Phthalocyanine with Unbalanced Rosin Added to the Grinding Step

A mixture of 91.0 g of crude copper phthalocyanine, 2.3 g of unbalanced rosin and 6.7 g of sodium formate is ground in a ball mill until the phase change indicates an α content of about 50 to about 75%. 50.0 g of the ground copper phthalocyanine mixture is added to 300 g of 2-ethyl hexanoic acid (2-EHA). The colored slurry is then stirred with a high speed mixer at about 80 ° C. for about 1 hour. The high speed mixer is then replaced with a paddle stirrer and the colored slurry is stirred at about 80 ° C. for about 2 hours. Finally, 219 g of 33% ammonium hydroxide solution is added. The slurry is filtered and washed with acetone until the pigment does not contain 2-EHA, and then the β pigment is dried at room temperature.

The heatset oil ink of Example 12 was evaluated according to Example 1.

In the tests of Examples 1 to 12, the variance was measured visually and graded compared to the standard level of the control, with + indicating a grade 1 superior to the standard, ++ indicating a grade 2 superior to the standard, ++ + Indicates that it is three grades superior to the standard, and = indicates that it is similar to the standard. Color intensity and gloss are measured visually and by instrument. Color intensity as defined herein refers to optical density / ink film weight, where the density is measured using a densitometer.

Example 1 Example 2 Example 3 Dispersion microscope Control = +++ Spotting and Filtration (First Pass) Control = +++ burglar Control = +10 Polish Control = ++

Table 1 shows the advantages of the oil ink system when rosin is added to the grinding step before conditioning treatment with solvent.

Example 4 Example 5 Example 6 Dispersion microscope Control = = Spotting and Filtration (First Pass) Control = = burglar Control +10 +5 Polish Control ++ ++

Table 2 shows the advantages of the oil ink system when rosin is added to the grinding step before conditioning with liquid amines in the presence of a surfactant.

Example 7 Example 8 Dispersion microscope Control = Spotting and Filtration (First Pass) Control + burglar Control +8 Polish Control +

Table 3 shows the advantages of the oil ink system when rosin is added to the grinding step before conditioning treatment with solvent.

Example 9 Example 10 Dispersion microscope Control ++ Strength (cover) Control +8 Glossy (cover) Control +++ Strength (uncovered) Control +5

Table 4 shows the advantages of liquid ink systems when rosin is added to the grinding step before conditioning treatment with solvents.

Example 11 Example 12 Dispersion microscope Control ++ Spotting and Filtration (First Pass) Control + burglar Control +4 Polish Control ++

Table 5 shows the advantages of the oil ink system when rosin is added to the grinding step before conditioning with carboxylic acid.

Claims (44)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete Dry or wet milling crude copper phthalocyanine with a natural or chemically modified resin and optionally a milling aid (a), (B) separating the ground material and The pulverized material is hydroxide in an aqueous polar solvent (the aqueous polar solvent consists of a ratio of water to polar solvent which prevents phase separation from occurring and the solvent is selected from a solvent capable of forming an azeotropic mixture with water). A process for producing pigmented copper phthalocyanine on beta crystals comprising the step (c) of conditioning in the presence of an anion. The method of claim 23, wherein the natural resin or chemically modified resin is rosin; Chemically modified rosin, including hydrogenated rosin, dehydrogenated rosin and unbalanced rosin; Dimerized or polymerized rosin; Partially esterified rosin; Of pigmented copper phthalocyanine on beta crystals, characterized in that it is selected from rosin or rosin derivatives and mixtures thereof which are not esterified or partially esterified with materials comprising maleic acid- or phenol-modified rosin and formaldehyde. Manufacturing method. 24. The method of claim 23, wherein the resin is present in an amount of from about 1 to about 15 weight percent based on the amount of crude copper phthalocyanine used. Claim 26 was abandoned upon payment of a registration fee. 24. Pigment copper phthalocyanine on beta crystals according to claim 23, characterized in that the grinding aid is selected from calcium chloride, sodium chloride, sodium sulfate, sodium formate, sodium acetate or other organic or inorganic salts, phthalimide or phthalic anhydride and mixtures thereof. Manufacturing method. 24. The method of claim 23, wherein the grinding aid is present in an amount from about 2 to about 15 weight percent based on the amount of crude copper phthalocyanine used. The process of claim 23, wherein the conditioning treatment is ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol or other lower alcohols; Ethyl acetate or other lower alkyl monocarboxylates; Acetone, methyl ethyl ketone, methyl isobutyl ketone or other dialkyl ketones; A process for producing pigmented copper phthalocyanine on beta crystals, characterized in that it is carried out using a mixture of water and a solvent selected from 2-methoxy ethanol, 2-ethoxy ethanol or other lower alkoxy alkanols. 24. The method of claim 23, wherein the conditioning solvent is present in an amount of from about 200 to about 1000 weight percent based on the weight of the ground material. The method of claim 23, Dry grinding the crude copper phthalocyanine with hydrogenated wood rosin and sodium formate, sodium chloride, sodium acetate or mixtures thereof (a), (B) separating the ground material by releasing it directly from the grinding device, The pulverized material is hydroxide in an aqueous polar solvent (the aqueous polar solvent consists of a ratio of water to polar solvent which prevents phase separation from occurring and the solvent is selected from a solvent capable of forming an azeotropic mixture with water). Conditioning in the presence of an anion (c) Heat-treating to convert copper phthalocyanine from α-form to β-form and treating the β-type copper phthalocyanine mixture with a dilute inorganic acid, removing the solvent, and then filtering and separating the β-type copper phthalocyanine product, followed by drying (e). . A β-type copper phthalocyanine product obtained by the method according to any one of claims 23 to 30. A β-type copper phthalocyanine product obtained by the process according to claim 23 for producing oil inks, gravure inks, paints and plastics. A method for producing a heatset oil ink using the β-type copper phthalocyanine product obtained by the method according to claim 23. A method for producing a liquid ink using the β-type copper phthalocyanine product obtained by the method according to claim 23. The beta of claim 23, wherein the derivative of copper phthalocyanine is added in any of steps (a) to (c) in an amount of about 20% by weight or less based on the weight of the pigment copper phthalocyanine. Process for producing pigmented copper phthalocyanine in crystalline phase. Claim 36 was abandoned upon payment of a registration fee. 36. The method of claim 35, wherein the amount of derivative of copper phthalocyanine added is from about 1 to about 5 weight percent based on pigment copper phthalocyanine. 36. The method of claim 35, wherein the derivative of copper phthalocyanine comprises: dimethylaminomethyl copper phthalocyanine or phthalimidomethyl copper phthalocyanine, wherein the number of substituents on the copper phthalocyanine molecule is 1-4; Sulfonated copper phthalocyanine; Or an amine salt of sulfonated copper phthalocyanine or a mixture thereof. 24. The pigment copper phthalocyanine on beta crystals according to claim 23, wherein the conditioning treatment is carried out using a mixture of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol or other lower alcohols with water. Manufacturing method. Claim 39 was abandoned upon payment of a registration fee. 39. The method of claim 38, wherein the conditioning treatment is performed using a mixture of water and n-butanol. Claim 40 was abandoned upon payment of a registration fee. 39. The process of claim 38, wherein the conditioning treatment is carried out using a mixture of water and isopropanol. 39. The method of claim 38, wherein the mixture of water and the lower alcohol contains at least 50% water by weight. Claim 42 was abandoned upon payment of a registration fee. 39. The method of claim 38, wherein the mixture of water and lower alcohol contains at least 75% by weight of water. 42. The method of claim 41, wherein the mixture of water and lower alcohol contains 80 to 98 weight percent water and 2 to 20 weight percent lower alcohol. Claim 44 was abandoned upon payment of a set-up fee. 44. The method of claim 43, wherein the mixture of water and lower alcohol contains 90 to 95 weight percent water and 5 to 10 weight percent lower alcohol.